Free-radical addition to olefins. Part VII. Addition of trichloromethyl radicals to chloro-olefins

D. P. Johari; H. W. Sidebottom; J. M. Tedder; J. C. Walton

doi:10.1039/J29710000095

Free-radical addition to olefins. Part VII. Addition of trichloromethyl radicals to chloro-olefins

D. P. Johari, H. W. Sidebottom, J. M. Tedder, J. C. Walton^*

^*Corresponding author for this work

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Abstract

The photochemically induced addition of bromotrichloromethane to a series of chlorine-substituted ethylenes has been studied in gas-phase experiments. Addition to a carbon atom of the olefin not carrying a chlorine atom leads to formation of a normal adduct. When the addition of trichloromethyl radicals or bromine atoms occurs at a carbon atom carrying a chlorine atom the major products are CCl₃CX=CX₂ and BrCX=CX₂ respectively, where CXCl=CX₂ represents the original chloro-ethylene. The rate of trichloromethyl radical addition to a chlorine-substituted site is slower than the rate of addition at =CF₂ and much slower than addition to =CH₂. Arrhenius parameters for the addition of CCl ₃· to the =CH₂ end of vinyl chloride have been measured: k(=CH₂) = (1.1 ± 0.4) × 10⁷ exp(-3400 ± 200)/RT

Original language	English
Pages (from-to)	95-99
Number of pages	5
Journal	Journal of the Chemical Society B: Physical Organic
DOIs	https://doi.org/10.1039/J29710000095
Publication status	Published - 1 Jan 1971

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title = "Free-radical addition to olefins. Part VII. Addition of trichloromethyl radicals to chloro-olefins",

abstract = "The photochemically induced addition of bromotrichloromethane to a series of chlorine-substituted ethylenes has been studied in gas-phase experiments. Addition to a carbon atom of the olefin not carrying a chlorine atom leads to formation of a normal adduct. When the addition of trichloromethyl radicals or bromine atoms occurs at a carbon atom carrying a chlorine atom the major products are CCl3CX=CX2 and BrCX=CX2 respectively, where CXCl=CX2 represents the original chloro-ethylene. The rate of trichloromethyl radical addition to a chlorine-substituted site is slower than the rate of addition at =CF2 and much slower than addition to =CH2. Arrhenius parameters for the addition of CCl 3· to the =CH2 end of vinyl chloride have been measured: k(=CH2) = (1.1 ± 0.4) × 107 exp(-3400 ± 200)/RT",

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T1 - Free-radical addition to olefins. Part VII. Addition of trichloromethyl radicals to chloro-olefins

AU - Johari, D. P.

AU - Sidebottom, H. W.

AU - Tedder, J. M.

AU - Walton, J. C.

PY - 1971/1/1

Y1 - 1971/1/1

N2 - The photochemically induced addition of bromotrichloromethane to a series of chlorine-substituted ethylenes has been studied in gas-phase experiments. Addition to a carbon atom of the olefin not carrying a chlorine atom leads to formation of a normal adduct. When the addition of trichloromethyl radicals or bromine atoms occurs at a carbon atom carrying a chlorine atom the major products are CCl3CX=CX2 and BrCX=CX2 respectively, where CXCl=CX2 represents the original chloro-ethylene. The rate of trichloromethyl radical addition to a chlorine-substituted site is slower than the rate of addition at =CF2 and much slower than addition to =CH2. Arrhenius parameters for the addition of CCl 3· to the =CH2 end of vinyl chloride have been measured: k(=CH2) = (1.1 ± 0.4) × 107 exp(-3400 ± 200)/RT

AB - The photochemically induced addition of bromotrichloromethane to a series of chlorine-substituted ethylenes has been studied in gas-phase experiments. Addition to a carbon atom of the olefin not carrying a chlorine atom leads to formation of a normal adduct. When the addition of trichloromethyl radicals or bromine atoms occurs at a carbon atom carrying a chlorine atom the major products are CCl3CX=CX2 and BrCX=CX2 respectively, where CXCl=CX2 represents the original chloro-ethylene. The rate of trichloromethyl radical addition to a chlorine-substituted site is slower than the rate of addition at =CF2 and much slower than addition to =CH2. Arrhenius parameters for the addition of CCl 3· to the =CH2 end of vinyl chloride have been measured: k(=CH2) = (1.1 ± 0.4) × 107 exp(-3400 ± 200)/RT

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Free-radical addition to olefins. Part VII. Addition of trichloromethyl radicals to chloro-olefins

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